Dichlor-dibrom-indigo and process of making same.



- and, the other,

t a blue solution in cold concentrated sulfuric I which are fast againstthe action of washing, 1

circumstances.

To all whom 'it may concern:

dichlor-dibrom-indigo in which the four new product symmetricalL.4.5.5-dichlor- UNITED STATES PATENT OFFICE.

PAUL vIK'ron VILLIGER, Ann PAUL NAWIASKY,2 ornnnwresHArEn-onran-mums,GERMANY, ASSIGNO'BS r0 BAmsoHE' ANILINUG: isone. EABBIK, orLUDWIGSHAFEN-ON-THE-RHINE, GERMANY, A ooRronA'rrort or GERMANY.

nrcnr-onrmnnon-mmco AND rnocnss or time sAmE.

Ho Drawing. Serial no; 528,563.

Application filed November 17, 1909.

The followinexample will serve to illustrate further tie nature of thisinvention and how it can' be carried into practical effect, but ourinvention is not confined to this example. The parts are by weight. Inthis example, we first, for the sake ,of convenience, describe theproduction of the methyl ester of chlor-brom-indoxyl carb'oxylic acidused in carrying out the process of the example. Introduce, :whilestirring, three hundred and thirty-seven parts of the methyl ester of3.4-hlor-brom phenyl= glycin-Q-carboxylic acid or ofBat-bromchlor-phenyl-glycin-2-carl)oxylic acid into a solution oftwenty-three parts of sodium in one thousand parts of methyl alcohol,and maintain the whole at seventy degrees centigrade for thirty minutes.Distil ofl the methyl 'alcohol,'d ige'st the residue with one thousandparts'of water and two hundred parts of thirty per -c entaacetic acid,and filter off, and wash and dry the chlor-bro'm- Be it known that we,PAUL J nuns, Ph. D., Vixron VILLIGER, Ph. 1)., and PAUL NAwI- ASKY, Ph.D., chemists, subjects the first and third of the Emperor of Austria,the second.a citizen of the Swiss Republic, residing atLudwigshafemon-the-Rhine, Germany, have invented new and usefulImprovements in Dichlor-Dibromslndigo and Processes of Making Same, ofWhich the following is a specification.

Our invention relates to the production of halogen atoms are in thepositions 4.4.5.5.

\Ve have invented a process for the .pro-' duction of ourdichlor-dibrom-indigo by the saponification and oxidation of an ester ofthe corresponding chlor-brom-indoxyl carboxylic acid. Thus, uponoperating in thisway upon the methyl ester of 4,5-chlor-bromv indoxylcarboxylic acid, or of 4:.5-bromchlor-indoxyl carboxylic acid, we obtainthe soluble in water and is diflicultly soluble in. most of the commonorganic solvents. can be converted into the corresponding indigocoloring matter dred and five parts of it with six thousand parts ofwater and five hundred and eleven parts of caustic while passing acurrent of the so'lution. Then add twelve thousand parts of boilingwater to the mixture, and

dibrom-indigo, of a constitution corresponding to the formula I NH NHfifth in which Hal and Hal are, the one, chlorin, bromin, It consistswhen dry ofa greenish blue powder which. yields hundred degrees cent-irade, until the oxidation is complete. If esired, the saponificaacid anda blue solution in hot dimethyl tion-can be carried out in the absenceof coal anilin. It differs from all known dichlors. dib'rom-indigoes inthat it dyes cotton from a. Now what we claim is a v vat exceptionallygreenish shades of blue, 1. The process of producing symmetricaldichlor-dibrom-indigo, in which the four halogen atoms are in thepositions 4.4:.55, by saponifying and oxidizing an ester of the*eorresponding chlor'brom-indox vl carboxlight, and chlorin. Moreover,the said shades when viewed by artificial light retain theirgreenishtint, whereas the other tetrahalogen indigoes hitherto described assumea reddish or violet-black tint under similar ylic acid substantially asdescribed.

2. As a new article of manufacture, symmetrical dichlor-dibrom1ndigo, inwhich the 'indoxyl carboxylic acid ester, which is 1nby boiling threehunpotash for thirty minutes, coal gas through four Quiet-:3

outside suction heads through Said diffusion eel; 1 the 'piieseuce oftwo subhalo en atoms are in the positions .1 rihingi J i 4415.5, whichconsists when (Try of a greenir'll blue powder cold concentratecSulfuric acid and a blue solution in hot dimethyl, aniling dyes cottonparticularly greenish shades of blue and contains both ch-lorin andbr0n1in..

In testimony whereof We have hereunto ion in Letters Patent No. 957,683.

Correct k 'PAUL JULIUS. I

- VIKTOR VILLIGER PAUL NAWIASKY.

i I W] i yields a blue solution in lVii'uesses J. Amie. LLOYD, W. W.SHMTDT.

, It is hereby certified that in Letters Patent No. 957,683, granted May10, 1910,

upon the application of PaulJuliu-s, Viktor Viiiiger, eusi PaulNawiasky, of Ludwigshafen-on-the-Rhine, Germany, for an improvement inDiehloi Dibrom-Indigo and ,Processes of Making Same, an error appears inthe printed specification requiring I correction as follows: Page 2,line 1, the words. outside suction heads through said difl'usion, shouldbe erased; and that the said Letters Patent shouldbe read with thiscorrection therein that the same may conform to the record of the casein the Patent Oflice. I

Signed and sealed this 5th day of July, A 1)., 1910.

[SEAL F. A. TENNANT,

Acting Obmmz'ssz'omr of Patents..

ion in Letters Patent No. 957,683.

Correct Quiet-:3

set

1 ghe urzseuce of two subin the positions yields a blue solution inlVitnesses J. Amie. LLOYD, W. W. Sruwror.

testimony whereof We have hereunto It is hereby certified that inLetters Patent No. 957,683, granted May 10, 1910,

upon the application of PaulJuliu-s, Viktor Viiiiger, exosi PoulNawiasky, of Ludwigsbafen-on-the-Rhine, Germany, for an improvement inDiehloefiibrom-Indigo and ,Processes of Making Same, an error appears inthe printed specification requiring I correction as follows: Page 2,line 1, the words. outside suction heads through said dif i'usion,should be erased; and that the said Letters Patent shouldbe read withthis correction therein that the same may conform to the record of theease in the Patent Oflice. I

Signed and sealed this 5th day of July, A 1)., 1910.

[SEAL F. A. TENNANT,

Acting Commissioner of Patents..

Correction in Letters Patent No. 957,683.

It is hereby certified that in Letters Patent No. 957,383, granted May10. 1910,

upon the application of Pan! Julius, Viktor Viiiigrfii :Eui Paul Nawiusku of Ludwigshafen-on-the-Rhine, Germany, for an improvement; in lishIor-Dibromlndigc and Processes of Making Same, an error appears inthe r-i mm specification requiring correction as follows: Page line 1,the word; outside suction heads through said diifusion. should beerased; and that the said Letters Patent should'he read with thiscorrection therein that the same may conform to the record of the easein the Patent Office.

Signed and sealed this 5th day of July, A. D., 1910.

[SEAL] F. A. TENNANT,

Acting Commissioner of Patents.

